CN-118084125-B - Application of zero-valent manganese sulfide in removing tetracycline in water body

Abstract

The invention belongs to the technical field of environmental remediation, and discloses application of zero-valent manganese sulfide in tetracycline removal. Experiments prove that the zero-valent manganese sulfide has remarkable adsorption effect on tetracycline antibiotics, and when the concentration of the tetracycline is 5-200 mg/L, the reaction temperature is 25 ℃, the initial pH value of the reaction is 10, and the adding amount of the zero-valent manganese sulfide is 1g/L, the adsorption efficiency of the zero-valent manganese sulfide on the tetracycline is more than 90%. The zero-valent manganese sulfide has obvious adsorption effect on the tetracycline antibiotics, and can be used as an adsorbent for removing the tetracycline antibiotics in the wastewater.

Inventors

• LONG JIANYOU
• DENG YIRONG
• LU HAIJIAN
• MO JIANYING
• LI HUOSHENG
• LUO DINGGUI
• ZHOU YING
• DENG ZIYI

Assignees

• 广州大学
• 广东省环境科学研究院

Dates

Publication Date

20260512

Application Date

20240402

Claims (2)

1. 1. The application of the zero-valent manganese sulfide in removing tetracycline in the water body is characterized in that the zero-valent manganese sulfide is added into the water body, and the adding amount of the zero-valent manganese sulfide in each milliliter of the water body is 0.5-2.0 milligrams; The preparation method of the zero-valent manganese sulfide comprises the steps of injecting NaBH 4 solution into MnSO 4 ·H 2 O solution at the speed of 10 mL/min -1 , stirring to prepare ZVMn suspension, adding Na 2 S·9H 2 O solution into the prepared ZVMn suspension, and synthesizing the zero-valent manganese sulfide, wherein the S/Mn molar ratio is 1.0 in the preparation method of the zero-valent manganese sulfide; The pH value of the water body with the tetracycline adsorbed by the zero-valent manganese sulfide is 10, and the temperature of the water body is 25 ℃.
2. 2. An adsorbent for removing tetracycline antibiotics from a body of water, said adsorbent comprising zero valent manganese sulfide as defined in claim 1.

Description

Application of zero-valent manganese sulfide in removing tetracycline in water body Technical Field The invention belongs to the technical field of environmental remediation, and particularly relates to application of zero-valent manganese sulfide in removal of tetracycline antibiotics in wastewater. Background The tetracycline antibiotics are widely applied to clinical medical treatment and livestock and poultry aquaculture industry as broad-spectrum antibiotics. The tetracycline antibiotics have common chemical structure precursors, mainly comprising tetracycline, aureomycin, oxytetracycline, demeclocycline, doxycycline, minocycline, tigecycline and the like. The large number of antibiotics used, abused and mishandled, results in frequent detection in environmental waters and soils. Animal husbandry and farming are one of the major sources of tetracycline contamination. Such antibiotics are often added to animal feed to increase growth rate and prevent disease. With the expansion of the breeding industry, a large amount of tetracycline antibiotics enter the animal body, and part of the unabsorbed antibiotics enter the environment along with the excreta of the animal. The method for removing the tetracycline antibiotics mainly comprises a high-grade oxidation method, an adsorption method, a coagulation method, a microorganism treatment method and the like. The traditional urban sewage treatment method mainly aims at removing suspended matters, organic matters, nitrogen, phosphorus and other components in sewage, and has relatively limited removal of trace drugs and antibiotics. The zero-valent metal has strong reduction performance, adsorption performance, applicability to various pollutants and the like, and is widely concerned in the aspects of environmental remediation and pollutant treatment. Although the zero-valent metal has good effect of degrading and removing antibiotics, the zero-valent metal before modification, such as zero-valent iron (ZVI), is easy to have the problems of passivation, poor stability, limited selectivity and the like. The vulcanization treatment of the zero-valent metal is an effective method for improving the performance, and can optimize the surface activity of the material, prevent the passivation and improve the stability. The application of zero-valent manganese sulfide in removing tetracycline antibiotics in wastewater is not seen in the prior art. Disclosure of Invention Treatment research on wastewater containing tetracycline antibiotics by virtue of zero-valent manganese (ZVMn) and vulcanization modification thereof has not been reported yet. The invention aims at exploring the removal effect of the zero-valent manganese (SZVMn) after vulcanization modification on the tetracycline in the water body. The invention provides application of zero-valent manganese sulfide in removing tetracycline antibiotics in water. The method comprises the steps of adding zero-valent manganese sulfide into a water body, wherein the adding amount of the zero-valent manganese sulfide in each milliliter of the water body is 0.5-2.0 milligrams. The preparation method of the zero-valent manganese sulfide comprises the steps of injecting NaBH 4 solution into MnSO 4·H2 O solution at the speed of 10 mL/min -1, stirring to obtain ZVMn suspension, adding Na 2S·9H2 O solution into the prepared ZVMn suspension, and synthesizing the zero-valent manganese sulfide, wherein the S/Mn molar ratio is 1.0 in the preparation method of the zero-valent manganese sulfide. The influence of the pH of the water body on the adsorption of the tetracycline by the zero-valent manganese sulfide is examined. The pH of the water body with the tetracycline adsorbed by the zero-valent manganese sulfide is preferably 4-10. Particularly, under alkaline conditions, the zero-valent manganese sulfide has higher adsorption rate to the tetracycline. Further preferably, the pH of the water body of the sulfidized zero-valent manganese adsorbed tetracycline is 10. The influence of the water temperature on the adsorption of the tetracycline by the zero-valent manganese sulfide is examined. The temperature of a suitable water body for adsorbing the tetracycline by the zero-valent manganese sulfide is 20-30 ℃. In particular, the water temperature of the tetracycline adsorbed by the zero-valent manganese sulfide is 25 ℃. The invention also provides an adsorbent for removing tetracycline antibiotics in water. The adsorbent comprises the zero valent manganese sulfide. The invention provides a preferred preparation method of the zero-valent manganese sulfide, which comprises the steps of flowing NaBH 4 solution into MnSO 4·H2 O solution through a peristaltic pump, wherein the speed is about 10 mL/min -1, and the stirring speed is 500rpm. After completion of inflow of MnSO 4·H2 O, stirring was continued for 30min, followed by precipitation for 10min. Likewise, SZVMn was synthesized by adding Na 2S·9H2 O solution to the prepared ZVMn suspens